Electrified microheterogeneous catalysis

ABSTRACT

In a system and method for enhancing chemical reactions, a reactant is brought in contact with a stable, non-soluble, porous, electronically non-conductive solid (reaction enhancer) in a fluidic medium to form a reaction mixture of low ionic strength. The reaction mixture so formed is then subjected to an electrifying force thereby enhancing the chemical reaction. Reaction products are then collected.

BACKGROUND OF THE INVENTION

The present invention relates to systems and methods for electrochemicalreactions and more particularly to catalysis in heterogeneous mediacontaining a dispersed solid and a liquid phase of low ionic strengthand in the presence of a low electrifying force.

In general, chemical reactions can by enhanced by manipulation ofrelevant local environmental conditions. The rate of the reaction mightincrease. This might also increase selectivity. Reactions which wouldotherwise have low yield or be prohibitively expensive might thus becommercially feasible.

Catalysts and enzymes substantially increase the rate of a reaction evenif present in small concentrations. The mechanism for this enhancementis usually expressed in terms of reducing the activation energy of thereaction. Not all chemical reactions can be so enhanced and they areoften enhanced only under a limited set of conditions.

Reactions may be enhanced by increasing the temperature or pressure. Themechanism for this enhancement is usually expressed in terms ofincreasing the likelihood of overcoming the activation energy. However,such enhancement may have undesirable aspects. For example, ecologicallydangerous but highly stable polychlorinated biphenyls (PCBs) may bedestroyed or detoxified by incineration at temperatures of between 800°and 3000° C. For such an operation, the energy costs are high and thegas and solid slag waste may still be environmentally unsafe.

Externally applied electric fields affect physical processes inelectrorheological fluids, such as slurries, and are used inelectrophoresis and field-flow fractionation to separate phases.Reaction rates of many chemical processes are known to be affected bythe presence of an electric field, as in Friedel-Crafts, decomposition,proton-transfer reactions, and field-induced effects at surfaces.However, these applications all involve high electric field strengths ofat least 1000 V/cm or even as high as several V/Å. It is undesirable touse such high fields because they might result in unwanted ionization(such as hydrolysis) or cause unwanted reactions to occur.

In electrolysis, electron transfer is a critical reaction step.Electrons are provided or removed at appropriate electrodes.Conventional electrolysis is typically carried out in media with highionic strength, usually provided by electrolytic solutions or moltensalts and with low applied voltages, typically under 2 volts. Theconcentration of ions and salts might be higher than that of reactants,thereby limiting desired reaction paths (or providing additionalunwanted reaction paths). Furthermore, the limited voltage window inelectrolysis due to the high ion and salt concentration could blockdesire reaction paths which might prefer larger voltage fields. In otherwords, certain reactions are unreachable with conventional electrolysis.

In dispersion electrolysis, metal spheres or supported-metal particlesare suspended in a high-impedance medium between feeder electrodes. Dueto the small size of the metal spheres and supported metal clusters, theunique properties of microelectrodes apply--electrolysis of smallamounts of material in the absence of supporting electrolyte salt.However, the suspension provides for a large number of particles so thatthe resulting macroscopic electrode area is large; this makes itpossible to electrolyze relatively large quantities of material at theensemble of microelectrodes. Since dispersion electrolysis is a form ofelectrolysis, electron transfer is a critical reaction step. Dispersionelectrolysis has thus far not been demonstrated for reactions other thanwater decomposition, hydrogen oxidation, and oxygen reduction.

SUMMARY OF THE INVENTION

It is an object of the present invention to enhance chemical reactionswithout requiring that the reaction environment be of high temperatureor high ionic strength.

It is a further object of the present invention to enhance chemicalreactions without requiring that the electrifying force be a highelectric field.

It is a still further object of the present invention to enhancechemical reactions wherein electron transfer need not necessarily be acritical reaction step.

These and other objects of the present invention are achieved bybringing a reactant in contact with a stable, non-soluble, porous,electronically non-conductive solid (reaction enhancer) in a fluidicmedium to form a reaction mixture of low ionic strength. The reactionmixture so formed is then subjected to an electrifying force therebyenhancing the chemical reaction. Reaction products are then collected.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a reactor for the practice of the present invention.

FIG. 2 is a current-time profile of ion-activation.

FIG. 3 shows the reactor used in the examples.

DETAILED DESCRIPTION OF THE INVENTION

In the practice of the present invention, chemical reactions areenhanced by contacting one or more reactants with solids known asreaction enhancers in a fluidic medium of low ionic strength and in thepresence of an electrifying force. The reaction enhancer of the presentinvention is a stable, non-soluble, porous, electronicallynon-conductive solid.

Stability and solubility of the reaction enhancer are determined interms of the medium and conditions in which the invention is practiced.As used herein, a stable solid does not appreciably react with thefluidic medium. Non-soluble means that no appreciable amount of thesolid dissolves in the fluidic medium. For example, β-alumina is notstable in water so it could not be used as a reaction enhancer in water.Electronic conductivity means direct current conductivity of electrons,as distinguished from ionic conductivity, and is to be avoided in orderto minimize unwanted effects under the influence of the electrifyingforce.

The preferred class of the subject reaction enhancer is zeolites.Zeolites have high adsorption or absorption, microporosity, stabilityand non-solubility in water, crystallinity, and are direct currentelectronic insulators. Because of their pores, channels or cages, theyact as molecular sieves and can distinguish between moleculesinteracting with them on the basis of size, shape and ionic nature. Manyzeolites have a strong ionic nature and contain charge-compensatingcations, typically alkali-metal or alkaline-earth, which can beion-exchanged for other cations such as metal cations or cationic metalcomplexes. They can provide a high ionic strength local environment. Asdiscussed further below, zeolites are capable of ion-activation.

In the present invention, a zeolite or other solid reaction enhancer influid suspension in the presence of an electrifying force has acatalytic effect.

As used herein, zeolites are defined as "crystalline molecular sievesconsisting of three-dimensional frameworks composed of tetrahedrallycoordinated atoms or ions bound to one another by oxygen." Kerr, G. T.,"Introduction," in Flank, W. H. and Whyte, T. E., Jr., eds.,"Perspectives in Molecular Sieve Science," (ACS Symposium Series 368):American Chemical Society: Washington, D.C., 1988, pg. xv., which isincorporated herein by reference. Traditional crystallinealuminosilicate zeolites, as well as substituted crystallinealuminosilicate structures, in which silicon or aluminum of atraditional zeolite is replaced by an isomorphic atom, meet thisdefinition. For example, aluminophosphates (ALPO),silicoaluminophosphates (SAPO), and metal substituted analogues of ALPOand SAPO structures (MAPO and MAPSO, respectively), are zeolitesaccording to this definition. These classes are explained further inRolison, D. R., "Zeolite-Modified Electrodes and Electrode-ModifiedZeolites," Chemical Review, 1990, vol. 90, pp. 867-878, which isincorporated herein by reference.

A subclass of reaction enhancer zeolites according to the presentinvention that are particularly important are "crystalline, hydratedaluminosilicates of group I and group II elements." Breck, D. W.,"Zeolite Molecular Sieves"; Wiley: New York, 1974, pp. 4-5, which isincorporated herein by reference. These crystalline hydratedaluminosilicates have been traditionally termed zeolites.

The following zeolites can be used as reaction enhancers in the presentinvention:

    ______________________________________                                        NAME      TYPICAL UNIT CELL CONTENTS                                          ______________________________________                                        Faujasite (Na.sub.2,K.sub.2,Ca,Mg).sub.29.5 [(AlO.sub.2).sub.59 (SiO.sub.2              ).sub.133 ].235 H.sub.2 O                                           X         Na.sub.86 [(AlO2).sub.86 (SiO.sub.2).sub.106 ].264 H.sub.2 O        Y         Na.sub.56 [AlO.sub.2).sub.56 (SiO.sub.2).sub.136 ].250 H.sub.2                O                                                                   Chabazite Ca.sub.2 [(AlO.sub.2).sub.4 (SiO.sub.2).sub.8 ].13 H.sub.2 O        Gmelinite Na.sub.8 [(AlO.sub.2).sub.8 (SiO.sub.2).sub.16 ].24 H.sub.2 O       ZK-5      (R,Na.sub.2).sub.15 [(AlO.sub.2).sub.30 (SiO.sub.2).sub.66 ].98               H.sub.2 O,                                                                    where R = [1,4-dimethyl-1,4-diazoniabicyclo                                   (2,2,2) octane].sup.2+                                              L         K.sub.9 [(AlO.sub.2).sub.9 (SiO.sub.2).sub.27 ].22 H.sub.2 O        Natrolite Na.sub.16 [(AlO.sub.2).sub.16 (SiO.sub.2).sub.24 ].16 H.sub.2                 O                                                                   Scolecite Ca.sub.8 [(AlO.sub.2).sub.16 (SiO.sub.2).sub.24 ].24 H.sub.2 O      Mesolite  Na.sub.16 Ca.sub.16 [(AlO.sub.2).sub.48 (SiO.sub.2).sub.72 ].64               H.sub.2 O                                                           Thomsonite                                                                              Na.sub.4 Ca.sub.8 [(AlO.sub.2).sub.20 (SiO.sub.2).sub.20 ].24                 H.sub.2 O                                                           Gonnardite                                                                              Na.sub.4 Ca.sub.2 [(AlO.sub.2).sub.8 (SiO.sub.2).sub.12 ].14                  H.sub.2 O                                                           Edingtonite                                                                             Ba.sub.2 [(AlO.sub.2).sub.4 (SiO.sub.2).sub.6 ].8 H.sub.2 O         Mordenite Na.sub.8 [(AlO.sub.2).sub.8 (SiO.sub.2).sub.40 ].24 H.sub.2 O       Dachiardite                                                                             Na.sub.5 [(AlO.sub.2).sub.5 (SiO.sub.2).sub.19 ].12 H.sub.2 O       Ferrierite                                                                              Na.sub.1.5 Mg.sub.2 [(AlO.sub.2).sub.5.5 (SiO.sub.2).sub.30.5                 ].18 H.sub.2 O                                                      Epistilbite                                                                             Ca.sub.3 [(AlO.sub.2).sub.6 (SiO.sub.2).sub.18 ].18 H.sub.2 O       Bikitaite Li.sub.2 [(AlO.sub.2).sub.2 (SiO.sub.2).sub.4 ].2 H.sub.2 O         A         Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].27 H.sub.2       ______________________________________                                                  O                                                               

These examples are explained further in Table 2.4 of Breck, supra, pg.49, which is incorporated herein by reference. Further examples ofzeolites which are effective as reaction enhancers in the presentinvention may be found in Breck, supra, which is incorporated herein byreference.

The preferred zeolites for use as reaction enhancers are faujasites andfaujasite-type structures (see Breck, supra at p. 92), such as zeolitesX and Y as well as the closely related zeolite A. It is believed thatsuch zeolites are effective because they have a 3-dimensional porositywith cages and channels. The invention has also been demonstrated for2-dimensionally porous synthetic mordenite (another zeolite), andnon-3-dimensionally porous zeolite L.

Zeolite crystals are generally of sub-micrometer to micrometer size.Reaction enhancers according to the present invention can be of anysize, although it is preferred that they be of sub-micrometer tomicrometer size.

Other types of material which can be used as reaction enhancers, if theyare stable, non-soluble, porous, and electronically non-conductivesolids, are organic compounds, such as polymers, and inorganicmaterials, such as metallocyano-derived lattices, borides, phosphides,nitrides, carbides, and silicides, and compounds and mixtures thereof.

Substances selected from the group consisting of aluminum oxide, siliconoxide, oxides of transition metals, and compounds and mixtures thereof,which are stable, non-soluble, porous, electronically non-conductivesolids can also be used as reaction enhancers according to the presentinvention. For example, γ-alumina, kaolin (an aluminosilicate that isnot a zeolite), silica, and mixtures thereof can be used as reactionenhancers. The following materials have been successfully used:γ-alumina, kaolin, and silica. α-alumina is a further example of areaction enhancer according to the present invention.

The medium in which the reaction occurs is fluidic. For example, it canbe a gas, a liquid, or a supercritical fluid. The preferred medium isliquid and the most preferred is aqueous (containing at least somewater).

The fluidic medium should be relatively free of contaminants, and of lowionic strength so as to minimize unwanted ions which might obscure thedesired reaction, and so as to minimize unwanted current when theelectrifying force is applied. As used herein, ionic strength is ameasure of the concentration of ions in solution. Water generally hasionic strength of under 10⁻⁶ molar. Ionic strength of under 0.025 molarsuffices, preferably under 0.005 molar.

The use of a reaction enhancer in the present invention does notpreclude the use of other additional catalysts or catalytic systems.They may be added to further increase the reaction rate or theselectivity of the reaction, which is especially desirable in synthesisreactions. A reaction catalyst or catalytic system may be supported onthe reaction enhancer. Such a supported catalyst or catalytic system ispreferably electronically nonconductive, so as to avoid dispersionelectrolytic effects which might interfere with operation of theinvention.

The fluidic medium may also be mixed with other additives. For example,one or more surfactants, wetting agents, emulsifying agents, andsolvents, such as acetone, might be added.

The fluidic medium-reactant-reaction enhancer reaction mixture (thereaction mixture) remains at low ionic strength, as that term wasdefined earlier.

The electrifying force can be any electrifying force known inelectrochemistry, such as applied electric potential, electric field, orcurrent. All of these quantities can be fixed or varied, and some or allof them can be controlled.

It is preferable to control the electric field or the potential acrossthe reaction mixture rather than the current. The potential can beadjusted to optimize the reaction being studied--different reactionswork best at different potentials. Typically, the average electric fieldacross the reaction mixture is kept under 1000 V/cm, and preferably,under 250 V/cm to avoid unwanted ionization and currents. Alternatively,the total potential drop across the reaction mixture is kept under 1000V and preferably, under 100 V. At large voltages, the reaction enhancermay become bound to the electrodes. The potential drop outside of thereaction mixture could be greater, for example, 6,000 V, but only thepotential drop across the reaction mixture is relevant herein.

Alternatively, the current through the reaction mixture is kept at nogreater than 2 Amp or the current density is kept at no greater than 10mA/cm². Limiting the current through the reaction mixture is importantfor several reasons. Firstly, high currents might heat the reactionmixture, thereby altering the reaction conditions and possibly causingreaction runaway. Secondly, high currents might interfere with thedesired reactions by forming and encouraging undesirable reactions.

There is no minimum (threshold) current--the process will effectivelywork without any current at all. Average electric fields across thereaction mixture which are significantly less than molecular electricfields (on the order of 1 V/Å) are effective. Preferably, the electricfield is at least 2.5 V/cm. In the most preferred embodiment, it isalways at least 25 V/cm. Preferably, the potential across the reactionmixture is at least 1 V and most preferably, at least 10 V. For eachreaction, the optimal minimum (threshold) potential or electric field,are to be empirically determined.

The electrifying force can be provided by a means external to thereaction mixture, or by electrodes in contact with the reaction mixture.The latter is preferable since much of the potential drop mightotherwise occur outside of the reaction mixture.

It is feasible to use any of the materials known in electrochemistry aselectrodes. However, material, such as nickel or lead, which oxidizeseasily would probably not be effective--it might go into the reactionmixture as ions. Electrodes containing material selected from the groupconsisting of platinum, gold, stainless steel, graphite, titanium,titanium oxide, ruthenium oxide, tantalum, and alloys, combinations andmixtures thereof are preferred. Films, especially platinum, can be usedon the electrodes. The best results have been obtained with electrodesthat are at least 50% platinum, and stainless steel has also been foundeffective. Excellent results have been obtained with a Nafion® (1100equivalent weight) coating on the cathode. Nafion® is a DuPont productwhich contains a selective path for ions and is water-permeable. Anyelectrode coating (on either or both electrodes) which provides a pathfor ions, and especially one which is water-permeable, can be used.

If a liquid reaction medium is selected, the reaction is preferablycarried out in a reactor 10 shown in FIG. 1. Reactor 10 comprises areaction chamber 12, contacting means 14, electrifying force means 16,and removal means (not shown) for removing a product (not shown).

The invention is practiced by introducing the fluidic medium 18,reaction enhancer 20, reactant 22, and any additives (not shown) to saidreaction chamber 12. The reactant 22 and reaction enhancer 20 arebrought into contact with each other by contacting means 14 to form areaction mixture. The reaction mixture is subjected to an electrifyingforce by electrifying force means 16 to produce at least one product.The product is removed from the reactor.

The contacting means 14 is means for providing contact between thereactant 22 and the reaction enhancer 20. As an example, the contactingmeans 14 can be a gas- or liquid-phased fluidized bed reactor containingthe reaction enhancer 20 so that the reactant 22 can be passed throughthe fluidized bed reactor.

In the preferred embodiment, the contacting means 14 is a means foruniformly dispersing the reactant 22 and reaction enhancer 20, insuspension or otherwise, in the fluidic medium 18, and bringing thereactant 22 and reaction enhancer 20 in contact with each other to forma reaction mixture. For example, the dispersion means can be means forpassing a gas through the reaction mixture, pumping or recirculating thereaction mixture, using an ultrasonicator, or mixing, such as bymechanical stirring, magnetic stirring, or other forms of agitation. Theexternal material providing the dispersion, such as the gas, the bladesor other mixing means, may be inert, or may take part in the reaction.

In one embodiment, the electrifying force means 16 includes a means formeasuring the current through said reaction mixture, which current isgenerally indicative of the progress of chemical reactions in thereaction mixture.

Typically, the reaction mixture formed by bringing at least one reactant22 in contact with the reaction enhancer 20 in a fluidic medium 18 is aslurry. This slurry is usually a heterogeneous medium containing adispersed solid (the reaction enhancer 20) and one or moreliquid-phases. In other words, it is a multiphasic system in which atleast one of the phases has a structure on the sub-micrometer tomicrometer scale.

The reaction mixture is of low ionic strength so as to minimize unwantedions which might obscure the desired reaction, and so as to minimizeunwanted background current under the influence of the electrifyingforce.

The optimum range of temperatures and pressures under which theinvention is carried out are to be empirically determined. Under theideal conditions, a balance is found between solubility, reaction rate,current, and volatility, all of which generally increase with increasedtemperature. It is preferable that the conditions be such that thefluidic medium is liquid, which for water at 1 atm, is between 0° C. and100° C. In the preferred embodiment, the pressure is about 1 atm and thetemperature is between about 0° C. and about 50° C. In a preferableembodiment, the temperature is below about 20° C. In a still morepreferable embodiment, the temperature is below about 10° C.

The concentration of reaction enhancer should be such that it does notappreciably increase the viscosity of the reaction mixture. Highviscosity affects transport mechanism and current. In the preferredembodiment, the molar concentration of the reaction enhancer is in therange of about 10⁻⁴ to about 10⁻² that of the reactant In the mostpreferred embodiment, it is about 10⁻³ that of the reactant. Typically,the reactant concentration is in the range of about 10⁻⁴ to about 10⁻¹M. In the most preferred embodiment, it is about 10⁻³ M.

The amount of time for running the operation is to be empiricallydetermined.

In the preferred embodiment, this invention is practiced by activatingthe reaction enhancer 20 with the fluidic medium 18 before bringing thereactant 22 and the reaction enhancer 20 in contact with each other. Inparticular, the reaction enhancer 20 is first dispersed in the fluidicmedium 18, thereby forming a preactivation mixture. The preactivationmixture is then activated by maintaining it (and continuing thedispersion of reaction enhancer 20 in it) for sufficient time to reachionic equilibrium at low ionic strength, thereby forming an activatedmixture. Activation may take hours for zeolites, for example. Thereactant 22 is then dispersed in said activated mixture and the reactant22 and the reaction enhancer 20 are brought in contact with each otherto form the reaction mixture. The reaction mixture is of low ionicstrength.

The activated mixture or reaction mixture, as well as the fluidic medium18, can contain catalysts or other additives, such as surfactants,wetting agents, emulsifying agents, and solvents, such as acetone. Theactivated mixture must be of low ionic strength, as defined earlier.

Activation affects not only the reaction enhancer 20 but the fluid inwhich it is dispersed. Accordingly, the activated mixture, and not justthe reaction enhancer 20, is activated. The activated mixture must, ofcourse, have low ionic strength (low solutional ionic concentration).

Activation of preactivation mixtures may be by ion-activation. Inion-activation, the thermodynamic process of reaching ionic equilibriumis achieved by application of an electrifying force. Ion-activationsubstantially speeds up the process--ionic equilibrium may be reached inminutes, rather than hours. Furthermore, although an activated mixtureactivated without application of an electrifying force and an activatedmixture activated by ion-activation might have the same measurable ionicconcentrations, the ion-activated mixture is often capable of greaterohmic currents and often results in reaction mixtures with greaterability to enhance reactions.

In general, an ion-activated mixture remains activated for a period oftime after the electrifying force is turned off. Typically, it can beused as an activated mixture as much as an hour later.

Ion-activation is typically practiced by applying the electrifying forceto the preactivation mixture by electrifying force means 16 under thesame conditions and with the same limitations as application of theelectrifying force means 16 to the reaction mixture.

The electrifying force means 16 typically has means for measuring thecurrent through said preactivation mixture, activated mixture, andreaction mixture, which current is indicative of the reactions occurringin the preactivation mixture, activated mixture, and reaction mixture.

The following alkali metal zeolites have been shown to ion-activateacross electrodes with applied potential differences of 10 to 100 volts,(25-250 V/cm average electric fields across the preactivation mixture):NaY, LiY, KY, RbY, CsY, synthetic sodium-compensated mordenite (NaLZ-M),KL, 1% Pt⁰ -NaY, 5% Pt⁰ -NaY and 10% Pt⁰ -NaY, NaA, NaX, and Pd^(II)Cu^(II) -NaY. In addition, HY, CaY, and NH₄ Y have been shown toion-activate.

NaY is the prototypical ion-activating reaction enhancer 20. Current isconsidered indicative of the ionic state, although in general it neednot be so. The current through the NaY aqueous preactivation mixturetypically rises until reaching a peak after about 1 minute. The currentthen typically declines to steady state several minutes later, formingan activated mixture. A current-time profile of such a response is shownin FIG. 2. However, ion-activation need not involve such a peak. Forexample, as also shown in FIG. 2, KL may ion-activate without the peak.

This invention is broadly effective in enhancing all chemical reactions.In particular, it is effective for oxidation, reduction, dehalogenation,decomposition. For organic reactants and in particular, for reactantscontaining at least one aromatic ring, it is particularly effective forhydrogenation, substitution, elimination, and decomposition.

The copending applications by inventors Debra R. Rolison and Joseph Z.Stemple entitled "Oxidation of Organic Materials by ElectrifiedMicroheterogeneous Catalysis," and "Decomposition of Halogenated andPolyhalogenated Organic Materials by Electrified MicroheterogeneousCatalysis," which applications are filed on the same day that thisapplication is filed, are incorporated herein by reference.

EXAMPLES

Having described the invention in general, the following examples aregiven as particular embodiments thereof and to demonstrate the practiceand advantages thereof. It is understood the examples are given by wayof illustration and are not intended to limit the specification or theclaims to follow in any manner.

EXPERIMENTAL APPARATUS

All of the following examples were performed using the reactor shown incross-section in FIG. 3. This reactor (30) is based on a cylindricalouter tube (32) with a side arm (34), the bottom of which cylindricaltube opens onto a tube (36) for inflow of gas. The bottom part of thetube above the inflow tube is sealed with a glass frit (38) of mediumporosity. An inner hollow cylindrical tube (40), sealed shut at thebottom but open on the top, is nested into the outer tube when theapparatus is assembled The outer electrode (42) is a 5-cm wide platinumfoil welded into a cylinder and fitted around the inner wall of theouter tube (32). The inner electrode (44) is a 5-cm wide platinum foilwelded in a cylindrical form about the outer surface of the inner tube(40). The dimensions of the apparatus are chosen so that when the innertube (40) is inserted in the outer tube (32), a toric area between theouter electrode (42) and the inner electrode (44) is formed, which toricarea is 5 cm high, with a gap of about 0.4 cm and constitutes thedispersion cell (46). The diameters of the outer electrode (42) andinner electrode (44) are about 3.0 cm and 2.2 cm, respectively. Thesefeeder electrodes (42,44) have surface areas of about 85 cm² in contactwith fluid in the dispersion cell (46).

When this experimental apparatus is used in the practice of the presentinvention, the outer electrode (42) is maintained at positive potentialwith respect to the inner electrode (44) at ground, and they are anodeand cathode, respectively. A d.c.-power supply (Kepco Model JQE orSorensen Model DCR-600-1.5B) (46) is used to so apply and maintain thevoltage across the electrodes. The cell current is determined from thevoltage drop measured across a 10.2 Ω, 160-watt resistor (48) in serieswith the cell.

The reaction enhancer and fluidic medium are combined in a vessel,shaken into slurry form, and then put in the dispersion cell (46).

Dispersion in the liquid medium is maintained by gas flow through tube(36) and through the frit (38) at the base of the dispersion cell (46)at the rate of about 80-240 mL/min. The gas flow remains on from aboutthe time the reaction enhancer - fluidic medium slurry is put in thedispersion cell (46) until the time the dispersion cell (46) contentsare removed. The gas may be an inert/non-reactive gas, such as helium,or one of the necessary reactants or a combination of both types ofgases in order to control or vary the concentration of the reactantgas(es).

Temperatures in the dispersion cell are monitored with a thermometerimmersed in silicone oil placed inside the inner cylindrical tube (40).

NaY zeolite used in the following examples was obtained in powder formfrom Strem. To assure a constant weight, it was used in fully hydratedform by water equilibrating it in an all-glass or plastic chamber oversaturated NH₄ Cl solution. In other words, this zeolite powder wasstored for at least a day in such a closed chamber containing asaturated aqueous solution of ammonium chloride.

The reaction enhancer is activated to form an activated mixture, bydispersing it in 18 Mohm-cm distilled, filtered and deionized water inthe cell and then applying a voltage with low potential gradient acrossthe electrodes while dispersion continues. The current flowing betweenthe electrodes is monitored until it reaches a steady state, whichusually occurs after about 5 to 10 minutes, depending on the actualconditions. The voltage is then turned off.

The organic compounds, reagents, reactants, and additional catalysts, ifany, are then added to the activated mixture in the dispersion cell (46)without an applied potential, and dispersed to form the reaction mixtureThe reaction is "run" by applying a voltage with low potential gradientacross the electrodes simultaneously with the continuing dispersion forsufficient time to form the reaction products.

The cell can be run with the downstream gas phase trapped in a lowtemperature trap, such as dry ice/acetone or liquid nitrogen, trapped ina bomb, or recycled into the dispersion cell for complete reaction, suchas by pressurizing the cell or using an internal cold finger to condensethe volatilized material. The trap (not shown) is coupled to side arm(34). After the reaction is run, the voltage across the electrodes isturned off. The liquid and the trapped gases are removed from the celland the trap, respectively, and analyzed to determine the identity andquantity of product and unreacted reactant. This analysis is performedby traditional analytical methods such as gas chromatography (with orwithout mass spectrometric detection), infrared spectroscopy, ionchromatography, liquid chromatography, or ¹ H nuclear magnetic resonancespectroscopy.

In examples 2a, 2b, 2c, 2d, and 3 below, only the cell contents wereanalyzed. They were transferred to a separatory funnel and extractedthree times with diethyl ether. The ether and aqueous layers wereseparated. Zeolites were filtered from the aqueous phase by vacuumfiltration. This remaining phase was examined for appearance and testedfor frothing when shaken. It was checked for chloride ion with the AgNO₃test (precipitation of AgCl). The ether layer (non-aqueous phase) wasdried over magnesium sulfate (MgSO₄) and filtered, and the excess etherwas removed with a roto-evaporator.

Example 1a

Selective partial oxidation of alkenes and, in particular, oxidation ofpropylene to acetone, by the mixed catalytic system of palladium (II)and copper (II) in the presence of oxygen and water.

In this example, a water jacket (not shown) surrounded the reactor (30)to control its temperature. The water jacket was maintained at -1° C.-0°C. The electrodes were platinum.

NaY zeolite as prepared above was ion-exchanged first in an aqueoussolution of PdCl₂ /NH₄ OH (to a weight loading of 1%), and then in anaqueous solution of CuCl₂ (6.5 weight %), to form a Pd^(II) Cu^(II) Ypowder. 53.6 mg of this zeolite powder was added to 20 mL of water andput in the dispersion cell. At about the time this preactivation mixturewas put in the dispersion cell, a gas flow of 67 mL/min helium wasturned on.

After the zeolite dispersed, thus forming the preactivation mixture, an80 V activation voltage was applied. The current peaked at 343 mA afterabout 60 sec, and then dropped to 44 mA steady-state current, thusforming the activated mixture. The voltage was then turned off.

The gas flow was then altered to 37 mL/min propene+20 mL/min oxygen+28mL/min helium. The reaction was then "run" by applying 20 V for 60minutes. The current rose from an initial 5.9 mA to 8.8 mA after 60minutes. The voltage was then turned off and the cell contents wereremoved.

After filtration, the aqueous phase was stored in air-tight glass vialssealed with a teflon-coated septum; these samples were then stored at 4°C. until analyzed by gas chromatography or gas chromatography - massspectrometry. Products were quantitated by comparison to standardsolutions of authentic compound material. Analysis showed the followingproducts: acetone - 5.2 μmol (76% selectivity), propionaldehyde - 0.18μmol (3% selectivity), propylene oxide - 1.38 μmol (20% selectivity),and acetaldehyde - 0.094 μmol (1% selectivity). The acetone topropionaldehyde ratio (mol/mol) was 29.

No products were found in the bomb. Therefore, all products were in theaqueous phase, and none were in the gas phase.

Without application of the potential and under these conditions, noproducts formed.

Example 1b

Selective partial oxidation of alkenes and, in particular, oxidation ofpropylene to propylene oxide, by the mixed catalytic system of palladium(II) and copper (II) in the presence of oxygen and water.

In this example, a water jacket (not shown) surrounded the reactor (30)to control its temperature. The water jacket was maintained at -1° C.-0°C. The electrodes were platinum.

NaY zeolite as prepared above was ion-exchanged in an aqueous solutionof PdCl₂ /NH₄ OH (to a weight loading of 1%). It was then dried at 100°C. and calcined in flowing oxygen at 300° C. for about 2 hours. Thismaterial was then ion-exchanged in an aqueous solution of CuCl₂ (6.5weight %), to form a Pd^(II) Cu^(II) Y calcined powder. 55.0 mg of thiscalcined zeolite powder was added to 20 mL of water and put in thedispersion cell. At about the time this preactivation mixture was put inthe dispersion cell, a gas flow of 100 mL/min helium was turned on.

After the zeolite dispersed, thus forming the preactivation mixture, an80 V activation voltage was applied. The current peaked at 270 mA afterabout 48 sec, and then dropped to 46 mA steady-state current, thusforming the activated mixture. The voltage was then turned off.

The gas flow was then altered to 30 mL/min propene+27 mL/min oxygen+31mL/min helium. The reaction was then "run" by applying 30 V for 60minutes. The current peaked on 4 regularly occurring occasions at 12 mA,and then reached 8.8 mA steady-state current at about 45 minutes. Afterthe reaction was run, the voltage was turned off and the cell contentswere removed.

Analysis showed the following products: propylene oxide - 2.4 μmol (71%selectivity), acetone - 0.4 μmol (12% selectivity), propionaldehyde -0.36 μmol (11% selectivity), and acetaldehyde - 0.22 μmol (7%selectivity). The propylene oxide to acetone ratio (mol/mol) was 6.

No products were found in the bomb. Therefore, all products were in theaqueous phase, and none were in the gas phase.

Without application of the potential and under these conditions, noproducts formed.

Example 2a

Dechlorination and deoomposition of chlorobenzene.

In this example, a water jacket (not shown) surrounded the reactor (30)to control its temperature. The water jacket was maintained at -1° C.-0°C. The electrodes were platinum. Dispersion was provided by a 140-160mL/min flow of helium.

53.4 mg of NaY zeolite powder prepared as above was added to 20 mL ofwater and put in the dispersion cell to form a zeolite suspensiondensity of 2.67 mg/mL. After the zeolite dispersed, thus forming thepreactivation mixture, a 30 V activation voltage was applied. Thecurrent peaked at 380 mA after about 40 sec, and then dropped to 270 mAsteady-state current over about 5 minutes, thus forming the activatedmixture. The voltage was then turned off.

0.1 mL of neat chlorobenzene, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed (about 5minutes after addition to the dispersion cell), thereby forming thereaction mixture, 30 V was applied. The current and temperature roseuntil after about 6 minutes, the current was greater than 300 mA and thetemperature was higher than 5° C. At that point, the voltage was loweredto 20 V and applied at that level for 84 additional minutes, for a totalreaction run time of 90 minutes. The voltage was then turned off. Thecontents of the dispersion cell dramatically changed color as thereaction was run.

The aqueous phase had a yellow-brown color, and frothed when shaken,indicating surfactancy caused by the presence of nonchlorobenzeneorganic species. The AgNO₃ test for chloride was positive, indicatingthe presence of chloride ions. The presence of chloride ions wasconfirmed by ion chromatography. Chlorobenzene, the reactant, does notgive a positive chloride test.

When no electric voltage is applied or no reaction enhancer is usedunder the above conditions, the aqueous phase is colorless, showsminimal frothing, and has negligible chloride, indicating that noreaction has occurred.

The ether extract evaporated to dryness.

Example 2b

Partial dechlorination of chlorobenzene and oxidation of benzene andunreacted chlorobenzene.

In this example, the reactor was not jacketed. It rested in an ice-waterbath and was maintained at 1°-10° C. The electrodes were platinum andthe inner (ground) electrode had a Nafion® film: coated on it by dippingthe electrode in a dilute solution of solubilized Nafion®, removing it,and letting it air-dry/evaporate. Dispersion was provided by a 140-160mL/min flow of helium.

50.8 mg of γ-alumina (Al₂ O₃) powder, used as received from Aesar, wasadded to 20 mL of water and put in the dispersion cell to form areaction enhancer suspension density of 2.540 mg/mL. After the aluminadispersed, thus forming the preactivation mixture, a 30 V activationvoltage was applied. The current did not peak, but reached 5 mAsteady-state current over about 5 minutes, thus forming the activatedmixture. The voltage was then turned off. This ion-activation proceduremay have been superfluous because of the minimal steady-state current.

0.1 mL of neat chlorobenzene, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed (about 5minutes after addition to the dispersion cell), thereby forming thereaction mixture, 30 V was applied. The current and temperature roseuntil after about 5 minutes, the current was greater than 400 mA and thetemperature was higher than 7° C. At that point, the voltage was loweredto 20 V and applied at that level for 70 additional minutes, for a totalreaction run time of 75 minutes. The voltage was then turned off. Thecontents of the dispersion cell dramatically changed color as thereaction was run.

The aqueous phase had a brown color. There was only minimal frothingwhen shaken. The AgNO₃ test for chloride was positive, indicating thepresence of chloride ions, as confirmed by ion chromatography.

When no electric voltage is applied or no reaction enhancer is usedunder the above conditions, the aqueous phase is colorless, showsminimal frothing, and has negligible chloride, indicating that noreaction has occurred.

The ether extract was yellow and evaporated to a yellow oil. Gaschromatography-mass spectrometry analysis showed 8 products The majoridentified products were chlorobenzene, chlorobenzoquinone, andbenzoquinone. Also present were chloro-(1,3)-benzenediol,chloro-(1,2)-benzenediol, and 1,2-benzenediol. There were also 2unidentified products.

These results are indicative of partial dechlorination of chlorobenzeneto benzene and oxidation of benzene and unreacted chlorobenzene to diolsand quinones.

Example 2c

Partial dechlorination of chlorobenzene and oxidation of benzene andunreacted chlorobenzene.

In this example, the reactor was not jacketed. It rested in an ice-waterbath and was maintained at 1°-10° C. The electrodes were platinum andthe inner (ground) electrode had a Nafion® film prepared as above.Dispersion was provided by a 140-160 mL/min flow of helium.

51.9 mg of kaolin powder, used as received from J. T. Baker, was addedto 20 mL of water and put in the dispersion cell to form a reactionenhancer suspension density of 2.595 mg/mL. After the kaolin dispersed,thus forming the preactivation mixture, a 30 V activation voltage wasapplied. The current did not peak, but reached 70 mA steady-statecurrent, thus forming the activated mixture. The voltage was then turnedoff.

0.1 mL of neat chlorobenzene, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed, therebyforming the reaction mixture, 30 V was applied. The current andtemperature rose until after about 5-10 minutes, the current was greaterthan 400 mA and the temperature was higher than 6° C. At that point, thevoltage was lowered to 20 V and applied at that level for a totalreaction run time of 80 minutes. The voltage was then turned off. Thecontents of the dispersion cell dramatically changed color as thereaction was run.

The aqueous phase had a light yellow color. There was slight frothingwhen shaken. The AgNO₃ test for chloride was positive, indicating thepresence of chloride ions, which was confirmed by ion chromatography.

When no electric voltage is applied or no reaction enhancer is usedunder the above conditions, the aqueous phase is colorless, showsminimal frothing, and has negligible chloride, indicating that noreaction has occurred.

The ether extract was yellow and evaporated to a yellow oil. Gaschromatography - mass spectrometry analysis showed 1 unidentified and 8identified products. The major identified products were chlorobenzene,chlorobenzoquinone, and benzoquinone. Also present werechloro-(1,2)-benzenediol, chloro-(1,3)-benzenediol, 1,2-benzenediol,1,3-benzenediol, and 2-methyl-2-pentenal.

These results are indicative of partial dechlorination of chlorobenzeneto benzene and oxidation of benzene and unreacted chlorobenzene to diolsand quinones.

Example 2d

Partial dechlorination of chlorobenzene and oxidation of benzene andunreacted chlorobenzene.

In this example, the reactor was not jacketed. It rested in an ice-waterbath and was maintained at 1°-10° C. The electrodes were platinum andthe inner (ground) electrode had a Nafion® film prepared as above.Dispersion was provided by a 140-160 mL/min flow of helium.

0.191 g of silica (SiO₂) powder, used as received from Aldrich, wasadded to 20 mL of water and put in the dispersion cell to form areaction enhancer suspension density of 9.550 mg/mL. After the silicadispersed, thus forming the preactivation mixture, a 30 V activationvoltage was applied. The current did not peak, but reached 35 mAsteady-state current, thus forming the activated mixture. The voltagewas then turned off. This ion-activation procedure may have beensuperfluous because of the minimal steady-state current.

0.1 mL of neat chlorobenzene, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed, therebyforming the reaction mixture, 30 V was applied. The current andtemperature rose until after about 34 minutes, the current was greaterthan 600 mA and the temperature was higher than 20° C. At that point,the voltage was lowered to 15 V and applied at that level for a totalreaction run time of 65 minutes. The voltage was then turned off. Thecontents of the dispersion cell dramatically changed color as thereaction was run.

The aqueous phase had a light yellow color. There was minimal frothingwhen shaken. The AgNO₃ test for chloride was positive, indicating thepresence of chloride ions, which was confirmed by ion chromatography.

When no electric voltage is applied or no reaction enhancer is usedunder the above conditions, the aqueous phase is colorless, showsminimal frothing, and has negligible chloride, indicating that noreaction has occurred.

The ether extract was yellow and evaporated to a yellow oil. Gaschromatography-mass spectrometry analysis showed 2 unidentified and 6identified products. The major identified product was chlorobenzene.Also present were chloro-(1,3)-benzenediol, chloro-(1,2)-benzenediol,chlorobenzoquinone, benzoquinone, and 1,2-benzenediol.

These results are indicative of partial dechlorination of chlorobenzeneto benzene and oxidation of benzene and unreacted chlorobenzene to diolsand quinones.

Example 3

Dechlorination and decomposition of polychlorinated biphenyl (PCB) andin particular, Aroclor® 6050, which consists of multiple polychlorinatedterphenyl congeners. Typically, destruction of Aroclor® 6050 does notoccur at temperatures lower than 1600° C.

In this example, the reactor was not jacketed. It rested in an ice-waterbath and was maintained at 1°-10° C. The electrodes were platinum.Dispersion was provided by a 180-240 mL/min flow of helium.

55.9 mg of NaY zeolite powder prepared as above, was added to 15 mL ofacetone and 5 mL of water and put in the dispersion cell to form azeolite suspension density of 2.795 mg/mL. After the zeolite dispersed,thus forming the preactivation mixture, a 30 V activation voltage wasapplied. The current peaked, then dropped to steady state, thus formingthe activated mixture. The voltage was then turned off.

0.2 mL of neat Aroclor® 6050, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed, therebyforming the reaction mixture, 30 V was applied. After about 38 minutes,the current began to increase and the cell contents began frothing anddarkening. At that point, the voltage remained at the same 30 V levelfor 84 additional minutes, for a total run time of 134 minutes. Thevoltage was then turned off.

The aqueous phase had a dark yellow-green color. After filtration, itwas a fine suspension. It showed good frothing when shaken, and thechloride test was positive. The presence of chloride ions was confirmedby ion chromatography. In other words, it contained chloride ion andorganic species which were not PCBs.

The ether extract was a dark violet-brown oil. Gas chromatography - massspectrometry analysis of it showed an almost complete loss of all theoriginal components with minimal levels remaining and with the additionof many new unidentified low molecular weight products. The absence ofreactant in the nonaqueous ether extract indicates that it reacted inthat PCBs and polychlorinated terphenyls would not have been lostthrough evaporation. Infrared spectroscopic analysis (relative tostarting material) showed a loss of aryl bands, the appearance ofesteric, carboxylic and alcoholic bands, and the near-total loss of thephenyl-phenyl bond moiety of the terphenyl. ¹ H-nuclear magneticresonance analysis (relative to starting material) showed the loss ofaryl protons and the appearance of alkyl protons. The infrared and NMRanalyses showed the creation of signals consistent with alkyl andesteric groups and the NMR analysis showed the loss of the proton signaldue to phenyl rings.

Decomposition of Aroclor® 6050 under these conditions does not occurunless there is both the NaY zeolite and an applied potential. Forexample, even after 29 hours of refluxing at 57° C. with NaY, theaqueous phase was colorless, had minimal frothing after shaking, andshowed only a trace of AgCl precipitate. The extracted nonaqueous phasewas a viscous straw-yellow oil, which was the color and viscosity of thestarting material. The contents did not change color during this entiretime.

Example 4

Dechlorination and defluorination of chlorofluorocarbons (CFCs) and inparticular, 1,1,2-trichlorotrifluoroethane (Freon® 113). As based onthis invention, destruction of Freon® 113 occurs at temperaturessubstantially lower than otherwise required for destructive incineration(above 500° C.).

In this example, the reactor was not jacketed. It rested in an ice-waterbath and was maintained at 1°-5° C. The electrodes were platinum.Dispersion was provided by a 100-140 mL/min flow of helium.

56.6 mg of NaY zeolite powder prepared as above was added to 20 mL ofwater and put in the dispersion cell to form a zeolite suspensiondensity of 2.830 mg/mL. After the zeolite dispersed thus forming thepreactivation mixture, a 20 V activation voltage was applied. Thecurrent peaked at 270 mA after about 80 seconds, then dropped to 200 mAsteady state, thus forming the activated mixture. The voltage was thenturned off. A dry ice-acetone gas-phase trap was prepared before runningthe reaction.

1.0 mL neat 0.42M Freon® 113, used as received, was then added to theactivated mixture in the dispersion cell. After it dispersed, therebyforming the reaction mixture, 20 V was applied. After about 10 minutes,the current increased slightly and light frothing in the cell contentswas noticeable. At that point, the voltage remained at the same levelfor 25 additional minutes, for a total run time of 35 minutes. Thevoltage was then turned off.

The trap contents were analyzed. It contained unreacted Freon® 113 whichhad been carried out of the dispersion cell by the sparging gas.

The cell contents were transferred to a separatory funnel and extractedthree times with diethyl ether. The ether extract evaporated to dryness.

The aqueous phase was colorless. The AgNO₃ test resulted in both AgCland AgF precipitates. The glass-etching test showed the presence of afluoride ion. The presence of chloride ions and fluoride ions wasconfirmed by ion chromatography.

It is understood that man other changes and additional modifications ofthe invention are possible in view of the teachings herein withoutdeparting from the scope of the invention as defined in the appendedclaims.

What is claimed is:
 1. A method for reacting at least one reactantcomprising the steps of:(a) bringing the at least one reactant incontact with at least one reaction enhancer in a fluidic medium to forma reaction mixture of low ionic strength, said at least one reactionenhancer being a stable, non-soluble, porous, electronicallynon-conductive solid; (b) subjecting said reaction mixture to anelectrifying force thereby forming a product by reaction of the at leastone reactant, said subjection being carried out in such a manner thatsaid at least one reaction enhancer enhances the reaction of the atleast one reactant to form the product; and (c) collecting the product.2. The method according to claim 1 wherein said reaction mixture hassolutional ionic concentration of less than 0.025 molar.
 3. The methodaccording to claim 2 wherein said reaction mixture has solutional ionicconcentration of less than 0.005 molar.
 4. The method according to claim1 wherein said fluidic medium is an aqueous liquid.
 5. The methodaccording to claim 4 wherein said at least one reaction enhancer isselected from the group consisting of metallocyano-derived lattices,borides, phosphides, nitrides, carbides, and silicides, compoundsthereof, and mixtures thereof.
 6. The method according to claim 4wherein said at least one reaction enhancer is selected from the groupconsisting of aluminum oxide, silicon oxide, oxides of transitionmetals, and mixtures thereof.
 7. The method according to claim 6 whereinsaid at least one reaction enhancer is selected from the groupconsisting of γ-alumina, α-alumina, kaolin, silica, and mixturesthereof.
 8. The method according to claim 4 wherein said at least onereaction enhancer is a zeolite selected from the group consisting offaujasite, faujasite-type structures, and zeolite A and mixturesthereof.
 9. The method according to claim 4 wherein said electrifyingforce produces an electric field in said reaction mixture.
 10. Themethod according to claim 4 wherein said electrifying force produces anelectric potential of at least 10 Volts across said reaction mixture.11. The method according to claim 5 wherein said electrifying forceproduces an average electric field of at most 1000 V/cm in said reactionmixture.
 12. The method according to claim 4 wherein said electrifyingforce produces a current across said reaction mixture.
 13. The methodaccording to claim 4 wherein said electrifying force produces a currentdensity of at most 10 mA/cm² in said reaction mixture.
 14. The methodaccording to claim 4 wherein said electrifying force is applied acrosstwo or more electrodes and at least one of said electrodes containmaterial selected from the group consisting of platinum, gold, stainlesssteel, graphite, titanium, titanium oxide, ruthenium oxide, tantalum,and mixtures thereof.
 15. The method according to claim 14 wherein atleast one of said electrodes is at least 50% platinum.
 16. The methodaccording to claim 14 wherein at least one of said electrodes is coatedwith a platinum film.
 17. The method according to claim 15 wherein atleast one of said electrodes is a cathode having a water-permeablecoating containing a path for ions.
 18. The method according to claim 4further comprising the step of dispersing the at least one reactant andsaid at least one reaction enhancer dispersed in said fluidic medium.19. The method according to claim 4 wherein said at least one reactionenhancer supports one or more reaction catalysts.
 20. The methodaccording to claim 19 wherein said reaction catalyst is electronicallynon-conductive.
 21. A method for reacting at least one reactantcomprising the steps of:(a) dispersing at least one reaction enhancer ina fluidic medium to form a preactivation mixture, said dispersaloccurring in the absence of the at least one reactant, said at least onereaction enhancer being a stable, non-soluble, porous, electronicallynon-conductive solid; (b) subjecting and preactivation mixture to afirst electrifying force in the absence of the at least one reactantuntil said preactivation mixture reaches ionic equilibrium, therebyforming an activated mixture of low ionic strength; (c) dispersing theat least one reactant in said activated mixture to form a reactionmixture of low ionic strength; (d) subjecting said reaction mixture to asecond electrifying force thereby forming a product by reaction of theat least one reactant, said subjection being carried out in such amanner that said at least one reaction enhancer enhances the reaction ofthe at least one reactant to form the product; and (e) collecting theproduct.
 22. The method according to claim 21 wherein said preactivationmixture and said reaction mixture each has solutional ionicconcentration of less than 0.025 molar.
 23. The method according toclaim 21 wherein said preactivation mixture and said reaction mixtureeach has solutional ionic concentration of less than 0.005 molar. 24.The method according to claim 21 wherein said fluidic medium is anaqueous liquid.
 25. The method according to claim 21 wherein said atleast one reaction enhancer is selected from the group consisting ofmetallocyano-derived lattices, borides, phosphides, nitrides, carbides,and silicides, compounds thereof, and mixtures thereof.
 26. The methodaccording to claim 24 wherein said at least one reaction enhancer isselected from the group consisting of aluminum oxide, silicon oxide,oxides of transition metals, and mixtures thereof.
 27. The methodaccording to claim 26 wherein said at least one reaction enhancer isselected from the group consisting of γ-alumina, α-alumina, kaolin,silica, and mixtures thereof.
 28. The method according to claim 24wherein said at least one reaction enhancer is a zeolite selected fromthe group consisting of faujasite, faujasite-type structures, andzeolite A and mixtures thereof.
 29. The method according to claim 24wherein said second electrifying force produces an electric field insaid reaction mixture.
 30. The method according to claim 24 wherein saidsecond electrifying force produces an electric potential across saidreaction mixture.
 31. The method according to claim 24 wherein saidsecond electrifying force produces an average electric field of at most1000 V/cm in said reaction mixture.
 32. The method according to claim 24wherein said second electrifying force produces a current across saidreaction mixture.
 33. The method according to claim 24 wherein saidsecond electrifying force produces a current density of at most 10mA/cm² in said reaction mixture.
 34. The method according to claim 24wherein said second electrifying force is applied across two or moreelectrodes and at least one of said electrodes contain material selectedfrom the group consisting of platinum, gold, stainless steel, graphite,titanium, titanium oxide, ruthenium oxide, tantalum, and mixturesthereof.
 35. The method according to claim 34 wherein at least one ofsaid electrodes is at least 50% platinum.
 36. The method according toclaim 34 wherein at least one of said electrodes is coated with aplatinum film.
 37. The method according to claim 34 wherein at least oneof said electrodes is a cathode having a water-permeable coatingcontaining a path for ions.
 38. The method according to claim 24 furthercomprising the step of dispersing the at least one reactant and said atleast one reaction enhancer dispersed in said fluidic medium.
 39. Themethod according to claim 24 wherein said at least one reaction enhancersupports one or more reaction catalysts.
 40. The method according toclaim 39 wherein said reaction catalyst is electronicallynon-conductive.
 41. The method according to claim 12 wherein saidelectrifying force produces an electric current of at most 2 Amp acrosssaid reaction mixture.
 42. The method according to claim 32 wherein saidsecond electrifying force produces an electric current of at most 2 Ampacross said reaction mixture.
 43. The method according to claim 15wherein said at least one of said electrodes containing at least 50%platinum is an anode.
 44. The method according to claim 35 wherein saidat least one of said electrodes containing at least 50% platinum is ananode.
 45. The method according to claim 16 wherein said at least one ofsaid electrodes having a platinum film is an anode.
 46. The methodaccording to claim 36 wherein said at least one of said electrodeshaving a platinum film is an anode.
 47. The method according to claim 9wherein said electrifying force produces an electric field of at least2.5 mV/cm in said reaction mixture.
 48. The method according to claim 29wherein said second electrifying force produces an electric field of atleast 2.5 mV/cm in said reaction mixture.
 49. The method according toclaim 9 wherein said electrifying force produces an electric field of atleast 25 mV/cm in said reaction mixture.
 50. The method according toclaim 29 wherein said second electrifying force produces an electricfield of at least 25 mV/cm in said reaction mixture.
 51. The methodaccording to claim 30 wherein said second electrifying force produces anelectric potential of at least 10 Volts across said reaction mixture.